Living polymer in situ system and method of use

Abstract

A kit for providing a polymerizable resin system is disclosed, which kit comprises a first Part A and a second Part B, which Part A and Part B upon mixing provides a working period of intermediate stage polymerization in which the mixture obtains a desired cohesiveness for a predetermined period of time. The first Part A comprises an acid and the second Part B comprises an organic compound that is water soluble or partially water soluble and that, in the presence of the acid, initiates curing of polymerizable monomer and/or resin that is present in Part A, Part B, or both. Also disclosed is a method of using the mixed composition as an adhesive, cement, glue, sealant, a base liner, a capping agent, a material for surface or structural repair and/or filling, an encasing material, a bodily implant, a dental material, and/or as a polymeric object having a living polymer surface property.

I claim: 
     
       1. A kit for providing a polymerizable resin system, which kit comprises a first Part A and a second Part B, at least one of which is a paste, which Part A and Part B upon mixing provides a working period of intermediate stage polymerization in which the mixture obtains a manipulative state of cohesiveness for a predetermined period of time, wherein the first Part A comprises one or more polymeric acids or one or more the acid-containing polymerizable monomers/oligomers, as well as combinations thereof; and the second Part B comprises an organic compound that is water soluble or partially water soluble and that, in the presence of the acid, can be ionized or solvated to initiate curing of one or more ethylenically unsaturated monomers or oligomers that is present in Part A, Part B, or both;
 wherein the organic compound is a salt of organic acid, an onium compound, protonated amines, and precursors thereof, as well as combinations thereof; and 
 wherein the one or more ethylenically unsaturated monomers and/or oligomers are chosen from the group consisting of acrylonitrile, acrylamide, (meth)acrylates, aldehydes, butadiene-1,3, ethylene, isoprene, methacrylic esters, methacrylamide, methyl styrene, styrene, vinyl esters, vinylidene chloride, and N-vinyl pyrrolidone, and combinations thereof; 
 wherein within 6 hours after mixing to form a paste, provides a working period of intermediate stage polymerization in which the paste obtains a cohesiveness characterized by a stress unit measurement of 0.5 to 2.0 kg/cm 2 , as measured with a penetrometer, which working period lasts for 45 seconds to 24 hours. 
 
     
     
       2. The kit of  claim 1  for providing a polymerizable resin system, wherein the second Part B comprises at least 0.2 wt. % of a salt of phenylglycine and derivatives thereof represented by the following structure (1) or organosulfur compounds represented by the following structure (2):
   R 1 C 6 H 4 NR 2 CH 2 COO − M + ,  (1)
 
 wherein R 1  is hydrogen or a substituted or unsubstituted alkyl group; C 6 H 4  is a phenyl group; R 2  is a hydrogen or a substituted or unsubstituted alkyl group optionally comprising a functional group that is vinyl, acrylate, or methacrylate; M +  is a metal cation to compensate electric charges; and
   R—S(O) n —O − X +   (2)
 
 
 wherein R is an organic radical; n=0, 1 or 2; and X +  is a metal cation to compensate electric charges, or combinations of compounds of structures (1) and (2). 
 
     
     
       3. The kit of  claim 2 , wherein the R group in organic compound (2) is a substituted or unsubstituted C 1 -C 10  alkyl or C 6 -C 12  aryl, wherein substituents are optionally selected from the group consisting of halogen, oxy, alkoxy, hydroxy, amino and/or imino radicals. 
     
     
       4. The kit of  claim 1  wherein the first Part A, the second Part B, or both, further comprises an inorganic filler in an amount of up to about ninety-five percent by weight of each component. 
     
     
       5. The kit of  claim 1  wherein the acid-containing polymerizable monomers/oligomers in first Part A comprises acrylic acid, methacrylic acid, 2-(methacryloyloxy)ethyl phosphate, bis(2-(methacryloyloxy)ethyl) phosphate, biphenyl dimethacrylate, ethylene glycol methacrylate phosphate, 4-methacryloxyethyl trimellitic anhydride, 4-methacryloxyethyl trimellitic acid, adduct reaction product of pyromellitic di-anhydride with 2-hydroxyethylmethacrylate, adduct reaction product of pyromellitic di-anhydride with glycerol dimethacrylate, or adduct reaction product of benzenetetracarboxylic acid di-anhydride with 2-(6-hydroxy-1-oxo-hexyloxy)ethyl methacrylate. 
     
     
       6. The kit of  claim 1  wherein the polymeric acid in first Part A comprises poly(acrylic acid) homopolymer or a copolymer. 
     
     
       7. The kit of  claim 1  wherein the acid-containing polymerizable monomers/oligomers in first Part A comprises 4-methacryloxyethyl trimellitic anhydride or 4-methacryloxyethyl trimellitic acid. 
     
     
       8. The kit of  claim 1  wherein the one or more ethylenically unsaturated monomers and/or oligomers present in Part A or Part B, or both, is an acrylate or a methacrylate. 
     
     
       9. The kit of  claim 1 , wherein the one or more ethylenically unsaturated monomers and/or oligomers present in Part A or Part B, or both, is selected from the group consisting of the condensation product of bisphenol A and glycidyl methacrylate, 2,2′-bis[4-(3-methacryloxy-2-hydroxy propoxy)-phenyl]-propane (hereinafter abbreviated “BIS-GMA”), urethane acrylates or diacrylates, urethane dimethacrylates (hereinafter abbreviated “UDMA”), triethylene glycol dimethacrylate (hereinafter abbreviated “TEGDMA”), polyethylene glycol dimethacrylate (hereinafter abbreviated “PEGDMA”), hexanedioldimethacrylate (hereinafter abbreviated “HDDMA”) and polycarbonate dimethacrylate (hereinafter abbreviated “PCDMA”); polylactide methacrylate (PLAMA), Glycerol Dimethacrylate (GDMA) and combinations thereof. 
     
     
       10. The kit of  claim 1 , wherein the first Part A, the second Part B, or both, further comprises photoinitiators and/or redox initiators, polymerization inhibitors, stabilizers, UV absorbers, radiopaque materials, fluorescent agents and therapeutic agents. 
     
     
       11. The dental composition made from the kit of  claim 10  wherein dental composition is a dental crown or bridge, an inlay/onlay, a root canal point, or post to restore a damaged tooth. 
     
     
       12. A dental composition made from the kit of  claim 1 , wherein dental composition is used as cement or restorative filling material, a bonding agent, a restorative composite, a root canal sealant, base liner, or a pulp capping agent. 
     
     
       13. A kit for providing a polymerizable resin system, which kit comprises a first Part A and a second Part B, at least one of which is a paste, which Part A and Part B upon mixing provides a working period of intermediate stage polymerization in which the mixture obtains a manipulative state of cohesiveness for a predetermined period of time, wherein the first Part A comprises one or more polymeric acids or one or more the acid-containing polymerizable monomers/oligomers, as well as combinations thereof; and the second Part B comprises an organic compound that is water soluble or partially water soluble and that, in the presence of the acid, can be ionized or solvated to initiate curing of one or more ethylenically unsaturated monomers or oligomers that is present in Part A, Part B, or both;
 wherein the acid-containing polymerizable monomers/oligomers comprise a methacrylate monomer having a phosphoric acid group and the methacrylate monomer having a phosphoric acid group is ethylene glycol phosphate methacrylate, hydroxyethyl methacrylate phosphate, or a combination thereof; 
 wherein the organic compound is a salt of organic acid, an onium compound, protonated amines, and precursors thereof, as well as combinations thereof; and 
 wherein the one or more ethylenically unsaturated monomers and/or oligomers are chosen from the group consisting of acrylonitrile, acrylamide, (meth)acrylates, aldehydes, butadiene-1,3, ethylene, isoprene, methacrylic esters, methacrylamide, methyl styrene, styrene, vinyl esters, vinylidene chloride, and N-vinyl pyrrolidone, and combinations thereof.